Cationic dyes containing an aryloxy group linked through a bridging radical to a quaternized nitrogen atom

ABSTRACT

Disclosed are basic dyes, e.g., azo dyes and anthraquinone dyes free from sulphonic acid groups and which contain, as characteristic group, a group of the formula ##STR1## in which R and R 1 , independently, are substituted or unsubstituted C 1-4  alkyl or are linked to form a ring, or 
     One of R and R 1  is --NH 2  or C 1-4  alkoxy, the other substituted or unsubstituted alkyl, 
     R 2  and R 3 , independently, are hydrogen or C 1-4  alkyl, 
     Y is a bridging group, 
     Q is unsubstituted or substituted phenyl, biphenylyl, naphthyl or ##STR2## in which R 7  is ##STR3## where R 8  ic C 1-4  alkyl, and 
     A -  is an anion. These dyes are useful for the dyeing and printing of polymers and copolymers of acrylonitrile and asymmetrical dicyanoethylene as well as polyesters and polyamides modified to contain acid groups. The dyes build-up well and exhibit good pH stability and stability to boiling. The obtained dyeings are level and possess good fastness to light, wet treatments, solvents, heat treatments and cross-dyeing.

This application is a continuation of application Ser. No. 383,878, filed on July 30, 1973 and now abandoned.

The invention relates to basic dyes free from sulphonic acid groups.

The invention provides basic dyes, free from sulphonic acid groups and which contain, as characteristic group, a group of formula T ##STR4## in which either R and R₁, which may be the same or different, each signify an alkyl radical of 1 to 4 carbon atoms, unsubstituted or substituted by hydroxy or phenyl,

or one of R and R₁ signifies-- NH₂ or C₁₋₄ alkoxy radical, the other having one of the above significances,

or R and R₁, together with the nitrogen atom to which they are attached, signify ##STR5## in which Ro signifies a C₁₋₄ alkyl or phenyl radical,

or the group ##STR6## signifies, as a whole, a radical of the formula ##STR7## in which the Ra's, independently, signify hydrogen or alkyl of 1 to 4 carbon atoms, and n signifies 1 or 2,

R₂ and R₃, which may be the same or different, each signify hydrogen or C₁₋₄ alkyl,

Y signifies a radical ##STR8## in which x signifies 1 to 6, R₄ signifies one of the above significances of R₂ and R₃, and R₅ signifies ##STR9## in which R₆ signifies hydrogen or C₁₋₄ alkyl,

A⁻ signifies an anion, and

Q signifies a radical of the formula ##STR10## in which R₉ signifies hydrogen; hydroxy; halogen; alkyl or alkoxy of 1 to 4 carbon atoms, unsubstituted or substituted by halogen, hydroxy, cyano, phenyl or phenoxy; cycloalkyl of 5 or 6 carbon atoms, unsubstituted or substituted by alkyl of 1 to 4 carbon atoms; trifluoromethyl; cyano; nitro; phenoxy; naphthyloxy; phenylazo; or a radical of the formula ##STR11## in which the Ro's, independently, signify C₁₋₄ alkyl or phenyl, and X signifies --CO-- or --SO₂ --,

R₁₀ signifies hydrogen, halogen or alkyl of 1 to 4 carbon atoms,

R₁₁ signifies C₁₋₄ alkyl, C₁₋₄ alkoxy, phenyl, phenoxy, halogen, ##STR12## a signifies 0, 1,2 or 3 or, where R₉ signifies halogen, 1,2,3,4 or 5, R₇ signifies ##STR13## in which R₈ signifies C₁₋₄ alkyl and R₈ ' signifies hydrogen or C₁₋₄ alkyl

Preferably, R and R₁ each signify C₁₋₄ alkyl, more preferably methyl or ethyl.

Preferably, R₂ and R₃, independently, signify hydrogen or methyl, more preferably hydrogen.

Preferably,

Y signifies ##STR14## in which R₄ ' signifies hydrogen or C₁₋₄ alkyl, more preferably hydrogen or methyl, most preferably hydrogen.

and x' signifies 1, 2 or 3, more preferably 1, or --CH═CH--CH₂ -- or --C.tbd.C--CH₂ -- or --CH₂ --O--CH₂ --CH₂ --.

Most preferably,

Y signifies --CH₂ --.

Preferably,

Q signifies an unsubstituted phenyl, naphthyl, biphenylyl dibenzofuranyl radical, or a phenyl radical substituted by halogen, preferably chlorine, C₁₋₄ alkyl or alkoxy, --CF₃, cyano or --NO₂, or a phenyl radical substituted by up to 5 chlorine atoms.

Most preferably Q signifies unsubstituted phenyl or 2-naphthyl, or phenyl substituted by up to 5 chlorine atoms.

As examples of anions A⁻ may be given the halides, such as chloride, bromide or iodide, sulphate, disulphate, methylsulphate, aminosulphate, perchlorate, carbonate, bicarbonate, phosphate, phosphormolybdate, phosphortungstenate, phosphortungstenmolybdate, formate, benzenesulphonate, naphthalenesulphonate, 4-chlorobenzenesulphonate, oxalate, maleimate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, malate, methanesulphonate or benzoate ions, or complex anions such as zinc chloride double salts, e.g. ZnCl₃ ⁻. The preferred anions are the halide methylsulphate ZnCl₃ ⁻ ions, acetate ions and sulphate ions.

As examples of the basic dyes provided by the invention may be given the azo series of dyes of formula Ia, ##STR15## in which D signifies a diazo component,

K signifies a coupling component,

w signifies a direct bond or a bridging group,

T is as defined above, and the group (s) W-T being bound to D and/or K,

t signifies 1 or 2.

As examples of preferred compounds of formula Ia, may be given the compounds of formula Iaa, ##STR16## in which K' signifies a radical of formula (m) or (n), ##STR17## in which R₁₈ signifies hydrogen, C₁₋₄ alkyl, preferably methyl, C₁₋₄ alkoxy, preferably methoxy, or halogen, preferably chlorine,

D' signifies a radical of formula (a), ##STR18## in which R₁₉ signifies hydrogen, nitro, halogen preferably chlorine or bromine, cyano, trifluoromethyl, C₁₋₄ alkylsulfonyl, preferably methylsulphonyl, phenylsulphonyl,, --CO--Ro, COORo, --CONHRo, alkyl of 1 to 4 carbon atoms, preferably methyl, or alkoxy of 1 to 4 carbon atoms, preferably methoxy or a radical --O₂ S--NR₂₁ R₂₂, wherein R₂₁ and R₂₂, independently, signify C₁₋₄ alkyl or are linked to form, together with the nitrogen, ##STR19## in which Rc signifies C₁₋₄ alkyl, preferably methyl,

R₁₁₉ and R₁₁₉ ', independently, signify hydrogen, nitro, halogen, preferably chlorine or bromine, cyano, C₁₋₄ alkyl, preferably methyl, trifluoromethyl, C₁₋₄ alkylsulphonyl or C₁₋₄ alkoxy, preferably methoxy,

R₂₁₉ signifies hydrogen, halogen, preferably chlorine, nitro or cyano, with the proviso that radical (a) contains no more than 3 substituents other than halogen, a radical of formula (b) or (c) ##STR20## in which R₃₁₉ signifies hydrogen, halogen, preferably chlorine, nitro, cyano, trifluoromethyl or C₁₋₄ alkylsulphonyl,

R₄₁₉ signifies hydrogen, halogen, preferably chloro, nitro, cyano, alkyl, preferably methyl, or C₁₋₄ alkoxy, preferably methoxy,

the R₂₀ 's independently, signify hydrogen, alkyl of 1 to 4 carbon atoms, preferably methyl, or alkoxy of 1 to 4 carbon atoms, preferably methoxy,

a radical of formula (d) ##STR21## in which R₂₃ signifies hydrogen, an unsubstituted phenyl radical; a phenyl radical substituted by C₁₋₄ alkyl, preferably methyl, cyano or nitro; a C₁₋₄ alkylsulphonyl radical; a C₁₋₄ alkylsulphoxide radical; a C₁₋₄ alkylthio radical; halogen, preferably chlorine, or C₁₋₄ alkyl, preferably methyl,

a radical of formula (e) ##STR22## in which R₂₃ ' signifies hydrogen, phenyl unsubstituted or substituted by C₁₋₄ alkyl, preferably methyl, cyano, nitro and halogen, preferably chlorine; or C₁₋₄ alkyl, preferably methyl,

a radical of formula (f) ##STR23## in which R₂₃ " signifies halogen, preferably chlorine,

R₂₃ ''' signifies cyano, --CONHRa in which Ra signifies hydrogen or C₁₋₄ alkyl, or --COORo, preferably cyano,

a radical of formula (g) ##STR24## Rg signifies halogen, preferably bromine, nitro or --CO--Ro, Rg' signifies halogen, preferably bromine,

a radical of formula (h) ##STR25## in which Rh signifies nitro, cyano, or trifluoromethyl, preferably nitro,

a radical of formula (i) ##STR26## in which Ri signifies nitro or cyano, preferably nitro,

a radical of formula (j) ##STR27## in which Rj and Rj'', independently, signify cyano, C₁₋₄ alkoxycarbonyl, preferably methoxycarbonyl, or --CONHRa,

Rj' signifies C₁₋₄ alkyl, preferably methyl, or phenyl,

a radical of formula (k) ##STR28## or a radical of formula (1) ##STR29## R₁₆ signifies hydrogen; alkyl of 1 to 4 carbon atoms, unsubstituted or substituted by halogen, hydroxy, cyano, phenyl, phenoxy, C₁₋₄ alkoxycarbonyl, C₁₋₄ alkylcarbonyloxy, C₁₋₄ alkoxy, benzoyloxy, ##STR30## or --CON(Ra)₂ in which the Ra's, independently, signify hydrogen or C₁₋₄ alkyl; or phenyl; R₁₆ preferably signifying an unsubstituted alkyl radical radical of 1 to 4 carbon atoms, more preferably methyl or ethyl,

R₁₇ signifies an alkylene radical of the formula ##STR31## or a radical ##STR32## in which R₂₅ signifies hydrogen or C₁₋₄ alkyl, preferably methyl, R₂₅ most preferably signifying hydrogen; and

T is as defined above.

In the compounds of formula Iaa, D' preferably signifies a radical of formula (a'), ##STR33## in which Ra' signifies hydrogen, halogen, preferably chlorine, nitro or cyano,

Ra" signifies hydrogen or halogen, preferably chlorine,

a radical of formula (") ##STR34## in which the Ra''''s, independently, signify hydrogen or halogen, preferably chlorine, and either R_(1a) and R_(2a), independently, signify an alkyl radical of 1 to 4 carbon atoms or are linked to form, together with the nitrogen atom, a morpholino radical;

a radical (d), in which R₂₃ signifies a phenyl radical or a 2-cyanophenyl radical; a radical (e), in which R₂₃ ' signifies a phenyl radical; a radical (i), in which Ri signifies nitro; a radical (f), in which R₂₃ " signifies chlorine and R₂₃ "' signifies cyano; a radical (g), in which Rg and Rg' both signify bromine; a radical (h), in which Rh signifies nitro; a radical (j), in which Rj and Rj" each signify cyano and Rj' signifies methyl, or in which Rj signifies methoxycarbonyl, Rj' signifies methyl and Rj" signifies cyano.

K' preferably signifies a radical of formula (m), most preferably a radical of formula (m), in which R₁₈ signifies hydrogen or methyl.

R₁₆ most preferably signifies an ethyl radical.

T preferably signifies a radical ##STR35## in which R',R₁ ',R₂ ',R₃ ', Y' and Q' correspond to the preferred significances of R, R₁, R₂, R₃, Y and Q, as given above.

As examples of other preferred compounds of formula Ia may be given the compounds of formula Iab, ##STR36## in which Ka' signifies a coupling component,

Z signifies a bridging group ##STR37## t signifies 1 or 2, preferably 1, and T is as defined above, preferably T', as defined above.

In the compounds of formula Iab, Ka' may, for example, be of the benzene, naphthalene, heterocyclic or aliphatic series. Suitable significances of Ka' will suggest themselves to those skilled in the art and, as will be appreciated, the particular significance of Ka' is of minor consequence in the invention. As examples of Ka' may be given the radicals of formulae ##STR38## in which R₁₈ ' and R₁₉ ', which may be the same or different, each signify hydrogen, or an alkyl radical of 1 to 4 carbon atoms unsubstituted or substituted by C₁₋₄ alkoxycarbonyl, benzoyloxy, phenoxy, halogen, preferably chlorine, hydroxy, cyano, C₁₋₄ alkoxy, C₁₋₄ alkylcarbonyloxy or N,N-di(C₁₋₄) alkylamino,

or one of

R₁₈ ' and R₁₉ ' signifies phenyl or cyclohexyl, the other having a significance as defined above,

or R₁₈ ' and R₁₉ ', together with the nitrogen atom to which they are attached, signify ##STR39## R₂₁ ' signifies a hydrogen atom, a C₁₋₄ alkyl or alkoxy radical or a halogen atom,

R₁₉ " signifies phenyl, C₁₋₄ alkyl, preferably methyl, unsubstituted or substituted by phenyl, e.g. benzyl,

R₂₀ " signifies hydrogen, phenyl or C₁₋₄ alkyl, preferably methyl,

R₂₂ ' signifies C₁₋₄ alkyl, preferably methyl,

the R₂₃ ''s which may be the same or different, each signifies C₁₋₄ alkyl, preferably methyl,

R₂₄ ' signifies hydroxy, amino, or monophenylamino,

R₂₅ ' signifies hydrogen or an alkyl radical of 1 to 4 carbon atoms, unsubstituted or substituted by C₁₋₄ alkoxy, preferably methoxy,

R₂₆ ' signifies hydrogen or halogen, e.g. chlorine or C₁₋₄ alkyl or alkoxy, preferably hydrogen,

R₁₈₁ and R₁₉₁, independently, signify hydrogen or C₁₋₄ alkyl, or one of R₁₈₁ and R₁₉₁ signifies hydrogen or C₁₋₄ alkyl, and the other has one of the above significances of R₁₈ ' or R₁₉ ' and

v signifies O or NH.

The preferred significances of Ka' are the above formulae (p), (r) and (y). In the formula (p), above, R₂₁ ' preferably signifies an alkyl radical of 1 to 4 carbon atoms, more preferably methyl, or a halogen atom, more preferably chlorine, R₁₈ ' and R₁₉ ' preferably signify hydrogen, C₁₋₄ alkyl, preferably ethyl, unsubstituted or substituted by cyano. In the formula (r), R₁₉ " preferably signifies C₁₋₄ alkyl, e.g., methyl, or phenyl, R₂₀ " preferably signifies C₁₋₄ alkyl, preferably methyl, or hydrogen, R₂₆ ' preferably signifies hydrogen or halogen, preferably chlorine. In the formula (y), R₂₃ ' preferably signifies C₁₋₄ alkyl, preferably methyl, phenyl, R₂₅ ' preferably signifies hydrogen, C₁₋₄ alkyl, unsubstituted or substituted by alkoxy, preferably methoxy; or phenyl, and v preferably signifies 0.

As examples of further compounds of formula Ia may be given the compounds of formula Iac. ##STR40## in which R_(6c) signifies hydrogen, halogen, preferably chlorine, C₁₋₄ alkyl, preferably methyl, or C₁₋₄ alkoxy, preferably methoxy,

R_(1c) and R_(2c), independently, signify hydrogen, alkyl of 1 to 4 carbon atoms, preferably methyl, or halogen, preferably chlorine, nitro, cyano or C₁₋₄ alkoxy, preferably methoxy,

R_(11c) signifies hydrogen, phenoxy, halophenoxy, preferably 4-chlorophenoxy, C₁₋₄ alkoxy, preferably methoxy, C₁₋₄ alkyl, preferably methyl, C₁₋₄ alkoxycarbonyl, preferably ethoxycarbonyl, phenylazo, C₁₋₄ alkylphenylazo, preferably 4-methylphenylazo,

with the proviso that

(i) when R_(11c) signifies phenylazo or C₁₋₄ -alkylphenylazo R_(2c) signifies hydrogen and R_(1c) and R_(6c), independently, signify hydrogen, C₁₋₄ alkyl, preferably methyl, C₁₋₄ alkoxy, preferably methoxy, more preferably R_(1c) and R_(6c) signifying hydrogen and (ii) the diazo component bears up to a maximum of 3 substituents,

R_(9c) signifies cyano, halogen, preferably chlorine, hydrogen or nitro, more preferably cyano,

R_(10c) signifies C₁₋₄ alkyl, preferably methyl, or phenyl,

u signifies 2 or 3, preferably 3.

T is as defined above, T preferably signifying T', as defined above.

As still further examples of formula Ia may be given the compounds of formula Iad, may be given the compounds of formula Iad, ##STR41## in which Hal signifies halogen, preferably chlorine,

Ka" signifies a radical (p), given above for Ka', and

T is as defined above.

In the compounds Iad, R₂₁ ' (in radical [p]), preferably signifies methyl or chlorine, R₁₈ ' and R₁₉ ', preferably signify, independently, hydrogen, ethyl or cyanoethyl. T preferably signifies T', above, more preferably ##STR42##

As further examples of compounds provided by the invention may be given the dyes of the anthraquinone series and of formula Ib, ##STR43## in which W signifies either a direct bond or a divalent bridging group,

A⁻ and T are as defined above,

z signifies 1 or 2, and when z signifies 2, the W's and T's may be the same or different, the W(s) being bound to ring Z₁₀ or Z₁₁, and

rings Z₁₀ and Z₁₁ are optionally further substituted.

Preferred compounds of formula Ib are the compounds of formula Ib'. ##STR44## in which R₄₀ signifies a group ##STR45## in which T is as defined above, R₄₅ signifies hydrogen or hydroxy, preferably hydrogen,

s signifies 1 or 2, or

R₄₀ signifies a hydroxy group or the group --NH--R₄₆, in which R₄₆ signifies hydrogen; C₁₋₄ alkyl, preferably methyl; cyclohexyl; phenyl, unsubstituted or substituted by up to two substituents, selected from C₁₋₄ alkyl, preferably methyl, C₁₋₄ alkoxy, benzyloxy and halogen, preferably chlorine,

R₄₁ signifies a group ##STR46## in which x6 signifies 2, 3 or 4, preferably 2 or 3, a group ##STR47## a group ##STR48## hydrogen, halogen, preferably bromine, cyano or --CONH₂, R₄₂ signifies a group ##STR49## a group in which

R₄₇ signifies halogen, preferably chlorine, or C₁₋₄ alkyl, preferably methyl,

q signifies 0, 1 or 2,

Y₂ signifies ##STR50## in which x2 signifies 1 or 2,

and x2' signifies 2 or 3, preferably 2; or a group --NH--R₄₆, in which R₄₆ is as defined above,

R₄₃ and R₄₄, which may be the same or different, each signify hydrogen, halogen, --NO₂, --NH₂ or --OH, a mono(C₁₋₄) alkylamino or di-(C₁₋₄) alkylamino radical, a monophenylamino, a phenoxy radical or a monocyclohexylamino radical, most preferably both signify hydrogen,

with the proviso that the compounds contain one or two T groups.

The preferred compounds of formula Ib' contain only one T group.

As examples of preferred compounds of formula Ib', may be given the compounds of formula Iba, ##STR51## in which R₅₈ signifies a C₁₋₄ alkyl radical, preferably methyl or ethyl,

R₆₉ signifies hydrogen, C₁₋₄ alkyl, preferably methyl or ethyl, C₁₋₄ alkoxy, preferably methoxy or ethoxy, benzyloxy or halogen, preferably chlorine,

R₇₀ signifies hydrogen, C₁₋₄ alkyl, preferably methyl or ethyl, C₁₋₄ alkoxy, preferably methoxy or ethoxy, or halogen, preferably chlorine

R₇₁ signifies methyl or ethyl,

Q" signifies an unsubstituted phenyl, biphenylyl, naphthyl or dibenzofuranyl radical or a phenyl radical substituted by halogen, preferably chlorine, cyano or nitro,

x5 signifies 2 or 3, and

x4 signifies 2, 3 or 4,

the compounds of formula Ibb, ##STR52## in which R₅₈, R₇₀, R₇₁, x4 and Q" are as defined above, and

R₇₂ signifies hydrogen, C₁₋₄ alkyl, e.g. methyl, ethyl, propyl or butyl, or cyclohexyl,

the compounds of formula Ibc, ##STR53## in which R₅₈, R₇₀, R₇₁, R₇₂, x4 and Q" are as defined above,

the compounds of formula Ibd, ##STR54## in which R₅₈, R₇₁, R₇₂, x4 and Q" are as defined above,

and the compounds of formula Ibe, ##STR55## in which R₅₅ signifies hydrogen or methyl, and R₅₈, R₇₁, R₇₂, x4 and Q" are as defined above.

The compounds of the invention may be produced in conventional manner from available starting materials. For example, the compounds can be produced by reacting a compound of formula II, ##STR56## in which R, R₁, R₂, R₃ and Q are as defined above,

with a dyestuff containing a leaving group such as the acid radical of an ester, e.g. a tosylate group, in conventional manner.

Where appropriate, the cleaving group may be an A⁻ yielding group or, if desired, the required A⁻ group may be introduced using conventional ion-exchange techniques.

Alternatively, for example, the compounds of the invention may be obtained by reacting a dyestuff containing the group ##STR57## with quaternising agent of the formula R₁ --A, in which R₁ is as defined above, and A is an A⁻ yielding group, in conventional manner.

The azo compounds of the invention may also be produced using conventional coupling techniques.

As examples of alkyl and alkoxy radicals of 1 to 4 carbon atoms, as used herein, may be given methyl, ethyl, n-propyl, isopropyl and n-butyl and the corresponding alkoxy radicals. Unless otherwise stated, the preferred such radicals are methyl, ethyl, methoxy and ethoxy, methyl and methoxy being most preferred. By the term halogen, as used herein, is meant chlorine, bromine and iodine; chlorine and bromine being preferred, chlorine being most preferred.

The compounds of formula I are useful as dyes. They may be converted into dyeing preparations, e.g. into stable, liquid or solid dyeing preparations, in conventional manner, e.g. by grinding or granulating or dissolving in conventional dyestuff solvents, if necessary with the addition of assistants such as stabilizers. Such preparations may be produced, for example, in accordance with French Pat. Nos. 1,572,030 and 1,581,900.

The compounds of formula I may be used in the dyeing or printing of textile substrates, whether in fibre, yarn or fabric form, which consist of or comprise homopolymers or co-polymers of acrylonitrile or asymmetrical dicyanoethylene. The dyeing of such substrates may be carried out in conventional manner.

The compounds of formula I may also be used for dyeing or printing substrates of synthetic polyamide or synthetic polyester fibres, modified by the introduction of acid groups. Polyamides of this type are described in Belgian Pat. No. 706,104 and polyester fibres of this type are described in U.S. Pat. No. 3,379,723. The dyeing of such substrates may be carried out in conventional manner. It is advantageous to dye in an aqueous, neutral or acid medium at from 60° C to the boil or at temperatures above 100° C under pressure.

The dyeings obtained with the compounds of formula I are level, have stable light fastness as well as good wet fastness properties, e.g. to washing, perspiration, sublimation, pleating, decatizing, pressing, steam, water, sea water, dry cleaning, cross-dyeing and solvents. The dyes are well soluble in water, show good compatibility with salt, good stability to boiling, good pH stability and partly reserve fibres other than those on which they are dyeable. Further, they possess good power of build-up in combination with other basic dyes.

The compounds, which have good solubility in organic solvents, may also be used for the dyeing of natural or synthetic resins in the mass, being incorporated therein in conventional manner, e.g. by intimate admixture therein, for example by milling, optionally with the use of a solvent.

It has been found that mixtures of two or more of the compounds of the present invention or of one of the compounds of the present invention and other cationic dyes can be used with advantage.

The following Examples, in which parts and percentages are by weight and temperatures are in degrees centrigrade, illustrate the invention.

EXAMPLE 1

17.2 Parts 1-amino-2-chloro-4-nitrobenzene are stirred into 30 parts concentrated hydrochloric acid, and then diluted with 200 parts ice and 100 parts water. Diazotization is accomplished according to a known method by the addition of a solution consisting of 7 parts sodium nitrite in 30 parts water. The resulting diazo solution is filtered and the excess sodium nitrite is decomposed with aminosulphonic acid. Finally the diazo solution is added dropwise to 37.8 parts of a coupling component of the formula ##STR58## dissolved in 200 parts water. After coupling, the pH of the solution is adjusted to a value from 4 to 5 by the addition of a 30% aqueous solution of sodium hydroxide and the resulting dye of the formula ##STR59## is filtered, washed with a 2% solution of sodium chloride, dried and ground. 49.5 Parts of a red-brown powder are obtained, which in an acid dye bath gives wet-fast and light-fast dyeings of a brownish-red shade on polyacrylonitrile fibres. Likewise on acid-modified polyester and polyamide fibres the same fast brownish-red dyeings are obtained.

The coupling component used above may be prepared in the following manner:

42.5 parts N,N-diethyl-N-2-phenoxyethyl amine (obtained from the reaction of 1-phenoxy-2-chloroethane with diethylamine) are heated to 80° to 90° in a nitrogen atmosphere, together with 36.8 parts N-ethyl-N-2'-chloroethylaniline in 90 parts water and 10 parts ethyl alcohol. The reaction solution is stirred for 3 hours in this temperature range and the pH is adjusted to between 8 and 9 by the addition of sodium hydroxide. The solution is diluted with 50 parts water, cooled to a temperature between 40° and 50°, extracted twice each time with 100 parts of toluene and the toluene phase is separated. The coupling component is obtained in the form of a 40% aqueous solution which may be used directly for the preparation of the dye.

EXAMPLE 2

Instead of the coupling component in Example 1, 45.4 parts of a compound of the formula ##STR60## is employed, using a similar process to yield a dye of the formula ##STR61## which, likewise, gives fast dyeings of a brownish-red shade on polyacrylonitrile and acid-modified polyester and polyamide fibres.

EXAMPLE 3

21 Parts 1-amino-2,6-dichloro-4-nitrobenzene are dissolved in 40 parts concentrated sulphuric acid at a temperature from 20° to 30° and is diazotized by the addition of a 40% solution of nitrosylsulfuric acid in concentrated sulphuric acid. The mixture is stirred into 100 parts water and 200 parts ice, and is stirred for 2 hours after the completion of the diazotization. After the decomposition of the excess nitrosylsulphuric acid with aminosulphuric acid, the cold diazo solution is added dropwise to an aqueous solution consisting of 39.9 parts of the coupling component of the formula ##STR62## and 400 parts water, and the pH of the solution is adjusted to 3 by the addition of a caustic soda solution. After the addition of 40 parts sodium chloride the dye of the formula ##STR63## is precipitated out, filtered by suction, washed with a 2% sodium chloride solution, dried and ground. 51.9 Parts of a yellow-brown powder are obtained, which powder gives light-fast and wet-fact dyeings of a yellow brown shade on polyacrylonitrile fibres dyed in an acid bath. A similar fast dyeing of a yellow brown shade was obtained on acid-modified polyester and polyamide fibres.

EXAMPLE 4

In place of the coupling component of Example 3, 41.8 parts of the compound of formula ##STR64## are used employing a similar process, and the dye of formula ##STR65## is obtained which gives fast yellow brown dyeings on polyacrylonitrile or acid-modified polyester or polyamide fibres.

EXAMPLE 5

In place of the coupling component of Example 4, 43.9 parts of the compound of formula ##STR66## is used employing a similar process and the dye of the formula ##STR67## is obtained, which likewise gives fast dyeings of a yellow brown shade on polyacrylonitrile and acid-modified polyester and polyamide fibres.

The structural composition of further dyes is shown in Table I. They may be produced in accordance with the procedure of Examples 1 to 5 and agree with the formula ##STR68## in which R₁ ' to R₅ ' have the significances given in the columns. A further column I indicates the dye shade on polyacrylonitrile. The anion A⁻ may be any one of those named in the foregoing description. The symbol K⁺ may stand for any of the groups K₁ to K₄₆ shown in Table A. These groups in any single dye may be exchanged for any of the further groups given for K₁ to K₄₆.

                  Table A                                                          ______________________________________                                         K.sub.1 signifies the group                                                            ##STR69##                                                              K.sub.2 signifies the group                                                            ##STR70##                                                              K.sub.3 signifies the group                                                            ##STR71##                                                              K.sub.4 signifies the group                                                            ##STR72##                                                              K.sub.5 signifies the group                                                            ##STR73##                                                              K.sub.6 signifies the group                                                            ##STR74##                                                              K.sub.7 signifies the group                                                            ##STR75##                                                              K.sub.8 signifies the group                                                            ##STR76##                                                              K.sub.9 signifies the group                                                            ##STR77##                                                              K.sub.10 signifies the group                                                           ##STR78##                                                              K.sub.11 signifies the group                                                           ##STR79##                                                              K.sub.12 signifies the group                                                           ##STR80##                                                              K.sub.13 signifies the group                                                           ##STR81##                                                              K.sub.14 signifies the group                                                           ##STR82##                                                              K.sub.15 signifies the group                                                           ##STR83##                                                              K.sub.16 signifies the group                                                           ##STR84##                                                              K.sub.17 signifies the group                                                           ##STR85##                                                              K.sub.18 signifies the group                                                           ##STR86##                                                              K.sub.19 signifies the group                                                           ##STR87##                                                              K.sub.20 signifies the group                                                           ##STR88##                                                              K.sub.21 signifies the group                                                           ##STR89##                                                              K.sub.22 signifies the group                                                           ##STR90##                                                              K.sub.23 signifies the group                                                           ##STR91##                                                              K.sub.24 signifies the group                                                           ##STR92##                                                              K.sub.25 signifies the group                                                           ##STR93##                                                              K.sub.26 signifies the group                                                           ##STR94##                                                              K.sub.27 signifies the group                                                           ##STR95##                                                              K.sub.28 signifies the group                                                           ##STR96##                                                              K.sub.29 signifies the group                                                           ##STR97##                                                              K.sub.30 signifies the group                                                           ##STR98##                                                              K.sub.31 signifies the group                                                           ##STR99##                                                              K.sub.32 signifies the group                                                           ##STR100##                                                             K.sub.33 signifies the group                                                           ##STR101##                                                             K.sub.34 signifies the group                                                           ##STR102##                                                             K.sub.35 signifies the group                                                           ##STR103##                                                             K.sub.36 signifies the group                                                           ##STR104##                                                             K.sub.37 signifies the group                                                           ##STR105##                                                             K.sub.38 signifies the group                                                           ##STR106##                                                             K.sub.39 signifies the group                                                           ##STR107##                                                             K.sub.40 signifies the group                                                           ##STR108##                                                             K.sub.41 signifies the group                                                           ##STR109##                                                             K.sub.42  signifies the group                                                          ##STR110##                                                             K.sub.43 signifies the group                                                           ##STR111##                                                             K.sub.44 signifies the group                                                           ##STR112##                                                             K.sub.45 signifies the group                                                           ##STR113##                                                             K.sub.46 signifies the group                                                           ##STR114##                                                        

    Table I                                                                        __________________________________________________________________________     Ex.                                                                                R.sub.1 '                                                                           R.sub.2 '                                                                          R.sub.3 '                                                                           R.sub.5 '                                                                           R.sub.4 '   K.sup.⊕                                                                       I                                        __________________________________________________________________________     6  Cl    H   H    H   C.sub.2 H.sub.5                                                                             K.sub.1                                                                            brownish-                                                                     red                                      7  "     H   H    H   "            K.sub.3                                                                           "                                        8  "     H   H    H   "            K.sub.4                                                                           "                                        9  "     H   H    H   "            K.sub.5                                                                           "                                        10 "     H   H    H   "            K.sub.6                                                                           "                                        11 "     H   H    H   "            K.sub.7                                                                           "                                        12 "     H   H    H   "            K.sub.8                                                                           "                                        13 "     H   H    H   "            K.sub.9                                                                           "                                        14 "     H   H    H   "            K.sub.10                                                                          "                                        15 "     H   H    H   "            K.sub.11                                                                          "                                        16 "     H   H    H   "            K.sub.12                                                                          "                                        17 "     H   H    H   "            K.sub.13                                                                          "                                        18 "     H   H    H   "            K.sub. 14                                                                         "                                        19 "     H   H    H   "            K.sub.15                                                                          "                                        20 "     H   H    H   "            K.sub.16                                                                          "                                        21 "     H   H    H   "            K.sub.17                                                                          "                                        22 "     H   H    H   "            K.sub.18                                                                          "                                        23 "     H   H    H   "            K.sub.19                                                                          "                                        24 "     H   H    H   "            K.sub.20                                                                          "                                        25 "     H   H    H   "            K.sub.21                                                                          "                                        26 "     H   H    H   "            K.sub.22                                                                          "                                        27 "     H   H    H   "            K.sub.23                                                                          "                                        28 "     H   H    H   "            K.sub.24                                                                          "                                        29 "     H   H    H   "            K.sub.25                                                                          "                                        30 "     H   H    H   "            K.sub.26                                                                          "                                        31 "     H   H    H   "            K.sub.27                                                                          "                                        32 "     H   H    H   "            K.sub.28                                                                          "                                        33 "     H   H    H   "            K.sub.29                                                                          "                                        34 "     H   H    H   "            K.sub.30                                                                          "                                        35 "     H   H    H   "            K.sub.31                                                                          "                                        36 "     H   H    H   "            K.sub.32                                                                          "                                        37 "     H   H    H   "            K.sub.33                                                                          "                                        38 "     H   H    H   "            K.sub.34                                                                          "                                        39 "     H   H    H   "            K.sub.35                                                                          "                                        40 "     H   H    H   "            K.sub.36                                                                          "                                        41 "     H   H    H   "            K.sub.37                                                                          "                                        42 "     H   H    H   "            K.sub.38                                                                          "                                        43 "     H   H    H   "            K.sub.39                                                                          "                                        44 "     H   H    H   "            K.sub.40                                                                          "                                        45 "     H   H    H   "            K.sub.41                                                                          "                                        46 "     H   H    H   "            K.sub.42                                                                          "                                        47 "     H   H    H   "            K.sub.43                                                                          "                                        48 "     H   H    H   "            K.sub.44                                                                          "                                        49 "     H   H    CH.sub.3                                                                           CH.sub.3     K.sub.1                                                                           "                                        50 "     H   H    "   "            K.sub.2                                                                           "                                        51 "     H   H    "   "            K.sub.13                                                                          "                                        52 "     H   CH.sub.3                                                                            "   "            K.sub.17                                                                          "                                        53 "     H   OCH.sub.3                                                                           "   "            K.sub.18                                                                          "                                        54 "     H   Cl   "   "            K.sub.44                                                                          yellowish-                                                                     orange                                   55 "     Cl  H    H   C.sub.2 H.sub.5                                                                             K.sub.1                                                                           yellowish-                                                                     brown                                    56 "     "   H    H   "            K.sub.2                                                                           "                                        57 "     "   H    H   "            K.sub.13                                                                          "                                        58 "     "   H    H   "            K.sub.17                                                                          "                                        59 "     "   H    H   "            K.sub.18                                                                          "                                        60 "     "   H    H   "            K.sub.19                                                                          "                                        61 "     "   H    H   "            K.sub.35                                                                          "                                        62 "     "   H    H   "            K.sub.43                                                                          "                                        63 "     "   H    H   "            K.sub.44                                                                          "                                        64 "     "   H    H   "            K.sub.12                                                                          "                                        65 "     "   H    H   "            K.sub.14                                                                          "                                        66 "     "   H    H   "            K.sub.15                                                                          "                                        67 "     "   H    H   "            K.sub.16                                                                          "                                        68 "     "   H    H   "            K.sub.36                                                                          "                                        69 "     "   H    H   "            K.sub.37                                                                          "                                        70 "     "   CH.sub.3                                                                            H   "            K.sub.1                                                                           "                                        71 "     "   "    H   "            K.sub.2                                                                           "                                        72 CN    H   H    H   "            K.sub.1                                                                           rubine                                   73 "     H   H    H   "            K.sub.2                                                                           "                                        74 "     H   H    H   "            K.sub.13                                                                          "                                        75 "     H   H    H   "            K.sub.17                                                                          "                                        76 "     H   H    H   "            K.sub.18                                                                          "                                        77 "     H   H    H   "            K.sub.19                                                                          "                                        78 "     H   H    H   "            K.sub.35                                                                          "                                        79 "     H   H    H   "            K.sub.43                                                                          "                                        80 "     H   H    H   "            K.sub.44                                                                          "                                        81 "     H   H    CH.sub.3                                                                           CH.sub.3     K.sub.2                                                                           "                                        82 NO.sub.2                                                                             Br  CH.sub.3                                                                            H   C.sub.2 H.sub.5                                                                             K.sub.1                                                                           violet                                   83 "     "   "    H   "            K.sub.2                                                                           "                                        84 "     "   "    H   "            K.sub.13                                                                          "                                        85 "     "   "    H   "            K.sub.17                                                                          "                                        86 "     "   "    H   "            K.sub.18                                                                          "                                        87 "     "   "    H   "            K.sub.19                                                                          "                                        88 "     "   "    H   "            K.sub.35                                                                          "                                        89 "     "   "    H   "            K.sub.43                                                                          "                                        90 "     "   "    H   "            K.sub.44                                                                          "                                        91 "     "   "    CH.sub.3                                                                           "            K.sub.2                                                                           "                                        92 "     "   H    H   "            K.sub.2                                                                           reddish-                                                                       violet                                   93 "     Cl  CH.sub.3                                                                            H   "            K.sub.2                                                                           violet                                   94 CF.sub.3                                                                             H   H    H   "            K.sub.2                                                                           rubine                                   95 SO.sub.2 CH.sub.3                                                                    H   H    H   "            K.sub.2                                                                           "                                        96 CH.sub.3                                                                             H   H    H   "            K.sub.2                                                                           brownish-                                                                      red                                      97 OCH.sub.3                                                                            H   H    H   "            K.sub.2                                                                           "                                        98 CN    CN  CH.sub.3                                                                            H   "            K.sub.2                                                                           bluish-                                                                        violet                                   99 NO.sub.2                                                                             NO.sub.2                                                                           "    H   "            K.sub.2                                                                           "                                        100                                                                               Cl    H   H    H   C.sub.4 H.sub.9                                                                             K.sub.2                                                                           brownish-                                                                      red                                      101                                                                               "     H   H    H   C.sub.2 H.sub.4 CN                                                                          K.sub.2                                     102                                                                               "     H   H    H   C.sub.2 H.sub.4COOC.sub.2 H.sub.5                                                           K.sub.2                                                                           "                                        103                                                                                ##STR115##                                        orange                   104                                                                                ##STR116##                                        red                      105                                                                                ##STR117##                                        bluish-  violet          106                                                                                ##STR118##                                        reddish- blue            107                                                                                ##STR119##                                        reddish- violet          __________________________________________________________________________

The structural composition of further dyes is shown in Table II. They can be produced in accordance with the procedure of Examples 3 to 5 and agree with the formula ##STR120## in which R₁ ' to R₈ ' and K⁺ have the significances as shown in the columns of the Table. A further column I shows the dye-shade on polyacrylonitrile. The anion A⁻ may be any one of those named in the foregoing description.

                                      Table II                                     __________________________________________________________________________     Ex.                                                                               R.sub.1 '                                                                         R.sub.2 '                                                                         R.sub.3 '                                                                          R.sub.5 '                                                                          R.sub.6 '                                                                         R.sub.7 '                                                                            R.sub.8 '                                                                            R.sub.4 '                                                                           K.sup.⊕                                                                       I                                      __________________________________________________________________________     108                                                                               --Cl                                                                              --Cl                                                                              H   H   H  --CH.sub.3                                                                           --CH.sub.3                                                                           --C.sub.2 H.sub.5                                                                   K.sub.1                                                                           golden-yellow                          109                                                                               "  "  H   H   H  "     "     "    K.sub.2                                                                           "                                      110                                                                               "  "  H   H   H  "     "     "    K.sub.12                                                                          "                                      111                                                                               "  "  H   H   H  "     "     "    K.sub.13                                                                          "                                      112                                                                               "  "  H   H   H  "     "     "    K.sub.14                                                                          "                                      113                                                                               "  "  H   H   H  "     "     "    K.sub.15                                                                          "                                      114                                                                               "  "  H   H   H  "     "     "    K.sub.16                                                                          "                                      115                                                                               "  "  H   H   H  "     "     "    K.sub.17                                                                          "                                      116                                                                               "  "  H   H   H  "     "     "    K.sub.18                                                                          "                                      117                                                                               "  "  H   H   H  "     "     "    K.sub.19                                                                          "                                      118                                                                               "  "  H   H   H  "     "     "    K.sub.35                                                                          "                                      119                                                                               "  "  H   H   H  "     "     "    K.sub.36                                                                          "                                      120                                                                               "  "  H   H   H  "     "     "    K.sub.37                                                                          "                                      121                                                                               "  "  H   H   H  "     "     "    K.sub.43                                                                          "                                      122                                                                               "  "  H   H   H  "     "     "    K.sub.44                                                                          "                                      123                                                                               "  "  --CH.sub.3                                                                         H   H  "     "     "    K.sub.2                                                                           reddish-                                                                       yellow                                 124                                                                               "  "  H   --CH.sub.3                                                                         H  "     "     --CH.sub.3                                                                          K.sub.2                                                                           "                                      125                                                                               "  "  H   H   H  --(CH.sub.2).sub.5 --                                                                      --C.sub.2 H.sub.5                                                                   K.sub.2                                                                           golden-yellow                          126                                                                               "  "  H   H   H  --C.sub.2 H.sub.4 --O--C.sub.2 H.sub.4--                                                   "    K.sub.2                                                                           "                                      127                                                                               "  "  H   H   H  --C.sub.4 H.sub.9                                                                    --C.sub.4 H.sub.9                                                                    "    K.sub.2                                                                           "                                      128                                                                               "  H  H   H   --Cl                                                                              --CH.sub.3                                                                           --CH.sub.3                                                                           "    K.sub.1                                                                           orange                                 129                                                                               "  H  H   H   "  "     "     "    K.sub.2                                                                           "                                      130                                                                               "  H  H   H   "  "     "     "    K.sub.12                                                                          "                                      131                                                                               "  H  H   H   "  "     "     "    K.sub.13                                                                          "                                      132                                                                               "  H  H   H   "  "     "     "    K.sub.14                                                                          "                                      133                                                                               "  H  H   H   "  "     "     "    K.sub.15                                                                          "                                      134                                                                               "  H  H   H   "  "     "     "    K.sub.16                                                                          "                                      135                                                                               "  H  H   H   "  "     "     "    K.sub.17                                                                          "                                      136                                                                               "  H  H   H   "  "     "     "    K.sub.18                                                                          "                                      137                                                                               "  H  H   H   "  "     "     "    K.sub.19                                                                          "                                      138                                                                               "  H  H   H   "  "     "     "    K.sub.20                                                                          "                                      139                                                                               --Cl                                                                              H  H   H   --Cl                                                                              --CH.sub.3                                                                           --CH.sub.3                                                                           --C.sub.2 H.sub.5                                                                   K.sub.35                                                                          orange                                 140                                                                               "  H  H   H   "  "     "     "    K.sub.36                                                                          "                                      141                                                                               "  H  H   H   "  "     "     "    K.sub.37                                                                          "                                      142                                                                               "  H  H   H   "  "     "     "    K.sub.43                                                                          "                                      143                                                                               "  H  H   H   "  "     "     "    K.sub.44                                                                          "                                      144                                                                               "  H  H   --CH.sub.3                                                                         "  "     "     --CH.sub.3                                                                          K.sub.2                                                                           "                                      145                                                                               "  H  H   H   "  --C.sub.2 H.sub.4 --O--C.sub.2 H.sub.4 --                                                  --C.sub.2 H.sub.5                                                                   K.sub.2                                                                           "                                      146                                                                               "  H  H   H   "  --(CH.sub.2).sub.5 --                                                                      "    K.sub.2                                                                           "                                      __________________________________________________________________________

EXAMPLE 147

17.8 Parts 4-amino-ω-dimethylaminoacetophenone (prepared by the reaction between 4 acetamino-ω-chloroacetophenone with dimethylamine and saponification of the acetamino group) are diazotized at 0° C employing conventional methods. The pH is adjusted to 8.0 by the addition of sodium carbonate and over the period of 1 hour a solution of 16.3 parts N,N-diethyl-m-toluidine, dissolved in 150 parts water and 50 parts glacial acetic acid, is added dropwise. After completion of the coupling reaction, the dye is salted out with sodium chloride, filtered, washed with a dilute brine solution, dried and ground, 17 Parts of the dye so obtained are dissolved in 75 parts isopropanol and 75 parts ethylmethylketone and over the period of 1 hour are mixed with 20.3 parts 1-phenoxy-4-chlorobut-2,3-ene. After 2 more hours at boiling temperature, the mixture is cooled to room temperature, the dye, after the addition of ether or dioxane, is filtered and washed with acetone and agrees with the formula ##STR121##

Fast red dyeings are obtained on polyacrylonitrile as well as on acid-modified polyester or polyamide fibres.

EXAMPLE 148

In place of the 1-phenoxy-4-chlorobut-2,3-ene used in Example 147, 18.6 parts of the compound of the formula ##STR122## (obtained by condensing sodium phenoxide with 1,4-dichlorobutane in the presence of sodium iodide), is employed using the procedure as described in Example 147 and the dye of the formula ##STR123## is obtained which likewise gives fast red dyeings on polyacrylonitrile as well as on acid-modified polyester and polyamide fibres.

The structural composition of further dyes is shown in the following Table III. The dyes can be produced in accordance with the procedure of Examples 147 and 148 and agree with the formula ##STR124## in which K⁺, K"' , X and have the significances as shown in the columns. A further column I indicates the shade of dyeing obtained on polyacrylonitrile. The anion A⁻ may be any one of those named in the foregoing description.

                  Table III                                                        ______________________________________                                         Ex.  X       Y     K.sup.⊕                                                                         K"               I                                     ______________________________________                                         149                                                                                  ##STR125##                                                                            1     K.sub.1                                                                              ##STR126##      red                                   150  "       1     K.sub.2                                                                             "                "                                     151  "       1     K.sub.13                                                                            "                "                                     152  "       1     K.sub.17                                                                            "                "                                     153  "       1     K.sub.18                                                                            "                "                                     154  "       1     K.sub.19                                                                            "                "                                     155  "       1     K.sub.35                                                                            "                "                                     156  "       1     K.sub.43                                                                            "                "                                     157  "       1     K.sub.44                                                                            "                "                                     158  SO.sub.2                                                                               1     K.sub.2                                                                             "                "                                     159                                                                                  ##STR127##                                                                            2     K.sub.2                                                                             "                orange                                160  "       1     K.sub.1                                                                              ##STR128##      red- dish- yellow                     161  "       1     K.sub.2                                                                             "                "                                     162  "       1     K.sub.1                                                                              ##STR129##      "                                     163  "       1     K.sub.2                                                                             "                "                                     164  "       1     K.sub.13                                                                            "                "                                     165  "       1     K.sub.17                                                                            "                "                                     166  "       1     K.sub.18                                                                            "                "                                     167  "       1     K.sub.19                                                                            "                "                                     168  "       1     K.sub.35                                                                            "                "                                     169  "       1     K.sub.43                                                                            "                "                                     170  "       1     K.sub.44                                                                            "                "                                     171  "       1     K.sub.1                                                                              ##STR130##      "                                     172  "       1     K.sub.2                                                                             "                "                                     172a "       1     K.sub.2                                                                              ##STR131##      "                                     173  "       1     K.sub.2                                                                              ##STR132##      "                                     174  "       1     K.sub.1                                                                              ##STR133##      yellow                                175  "       1     K.sub.2                                                                             "                "                                     176  "       1     K.sub.16                                                                            "                "                                     177  "       1     K.sub.17                                                                            "                "                                     178  "       1     K.sub.18                                                                            "                "                                     179  "       1     K.sub.19                                                                            "                "                                     180  "       1     K.sub.35                                                                            "                "                                     181  "       1     K.sub.43                                                                            "                "                                     182  "       1     K.sub.44                                                                            "                "                                     183  "       1     K.sub.12                                                                            "                "                                     184  "       1     K.sub.1                                                                              ##STR134##      "                                     185  "       1     K.sub.2                                                                             "                "                                     186  "       1     K.sub.1                                                                              ##STR135##      "                                     187  "       1     K.sub.2                                                                             "                "                                     188  "       1     K.sub.2                                                                              ##STR136##      "                                     189  "       1     K.sub.2                                                                              ##STR137##      "                                     ______________________________________                                    

EXAMPLE 190

25.6 parts of 4-amino-4'-chloro-diphenyletherchlorohydrate are dissolved in 300 parts water and are diazotized, after the addition of 18 parts of 30% hydrochloric acid with 6.9 parts sodium nitrite, according to conventional methods. This diazo solution is added to 24.7 parts of the coupling component of the formula ##STR138## dissolved in 200 parts 2% hydrochloric acid. After completion of the coupling, the dye of the formula ##STR139## is salted out with sodium chloride at 60°, filtered and dried. 15 Parts of the dye so obtained are diluted with 75 parts isopropylalcohol and 75 parts ethylmethylketone, mixed with 9.0 parts 2-phenoxy-1-chloroethane and the mixture is heated for 3 hours. After cooling, the quaternated dye of the formula ##STR140## is precipitated out with ether, dioxane or acetone. After filtering, drying and grinding a dye is obtained which gives light-fast and wet-fast dyeings of a reddish-yellow shade on polyacrylonitrile, acid-modified polyesters and polyamide fibres.

The coupling component may be prepared by condensing cyanoacetic acid-3-dimethylamino-n-propylamide with ethyl acetate.

EXAMPLE 191

In place of the 2-phenoxy-1-chloroethane quaternating agent of Example 190, the compound of the formula ##STR141## is used, employing the same method, to obtain the dye of the formula ##STR142## which dye likewise gives fast reddish-yellow dyeings on polyacrylonitrile as well as on acid-modified polyester and polyamide fibres.

The structural composition of further dyes is shown in the following Table IV. They may be prepared according to the procedure of Examples 190 and 191 and agree with the formula ##STR143## in which R₁ ', R₂ ', R₆ ', R₉ ' to R₁₁ ', x and K⁺ have the significances as shown in the columns. A further column I indicates the dye shade on polyacrylonitrile. The anion A⁻ may be any one of those named in the foregoing description.

                                      Table IV                                     __________________________________________________________________________     Ex.                                                                               R'.sub.1                                                                           R'.sub.2                                                                          R'.sub.6                                                                          R'.sub.9                                                                           R'.sub.10                                                                          X K.sup.⊕                                                                       R'.sub.11 I                                          __________________________________________________________________________     192                                                                               H   H  H  CN  CH.sub.3                                                                           3 K.sub.1                                                                            ##STR144##                                                                              yellow                                     193                                                                               H   H  H  "   "   3 K.sub.2                                                                           "         "                                          194                                                                               H   H  H  "   "   3 K.sub.12                                                                          "         "                                          195                                                                               H   H  H  "   "   3 K.sub.13                                                                          "         "                                          196                                                                               H   H  H  "   "   3 K.sub.14                                                                          "         "                                          197                                                                               H   H  H  "   "   3 K.sub.15                                                                          "         "                                          198                                                                               H   H  H  "   "   3 K.sub.16                                                                          "         "                                          199                                                                               H   H  H  "   "   3 K.sub.17                                                                          "         "                                          200                                                                               H   H  H  "   "   3 K.sub.18                                                                          "         "                                          201                                                                               H   H  H  "   "   3 K.sub.19                                                                          "         "                                          202                                                                               H   H  H  "   "   3 K.sub.35                                                                          "         "                                          203                                                                               H   H  H  "   "   3 K.sub.36                                                                          "         "                                          204                                                                               H   H  H  "   "   3 K.sub.43                                                                          "         "                                          205                                                                               H   H  H  "   "   3 K.sub.44                                                                          "         "                                          206                                                                               Cl  H  Cl "   "   3 K.sub.2                                                                           H         "                                          207                                                                               "   H  "  "   "   3 K.sub.17                                                                          H         "                                          208                                                                               "   H  "  "   "   3 K.sub.19                                                                          H         "                                          209                                                                               "   H  "  "   "   3 K.sub.43                                                                          H         "                                          210                                                                               H   H  H  "   "   3 K.sub.2                                                                            ##STR145##                                                                              golden yellow                              211                                                                               H   H  H  "   "   3 K.sub.17                                                                          "         "                                          212                                                                               H   H  H  "   "   3 K.sub.43                                                                          "         "                                          213                                                                               CH.sub.3                                                                           H  H  "   "   3 K.sub.2                                                                            ##STR146##                                                                              reddish- yellow                            214                                                                               H   H  Cl "   "   3 K.sub.2                                                                           CH.sub.3 O                                                                               "                                          215                                                                               H   H  H  "   "   3 K.sub.2                                                                           H         greenish-                                                                      yellow                                     216                                                                               H   H  Cl "   "   3 K.sub.2                                                                           CH.sub.3  yellow                                     217                                                                               H   Cl "  "   "   3 K.sub.2                                                                           H         greenish-                                                                      yellow                                     218                                                                               H   H  "  "   "   3 K.sub.2                                                                           H         "                                          219                                                                               H   H  "  "   "   3 K.sub.2                                                                           COOC.sub.2 H.sub. 5                                                                      "                                          220                                                                               H   H  H  "   "   2 K.sub.2                                                                            ##STR147##                                                                              yellow                                     221                                                                               H   H  H  H   "   3 K.sub.2                                                                           "         "                                          222                                                                               H   H  H  Cl  "   3 K.sub.2                                                                           "         "                                          223                                                                               H   H  H  NO.sub.2                                                                           "   3 K.sub.2                                                                           "         "                                          224                                                                               H   H  H  CN                                                                                  ##STR148##                                                                        3 K.sub.2                                                                           "         "                                          __________________________________________________________________________

EXAMPLE 225

40 Parts nitrosylsulphuric acid with a nitric acid strength of 6.4% is stirred with a mixture of 50 parts acetic acid and 50 parts phosphoric acid under cooling at a temperature from -5° to 0°. 17.7 Parts of 5-amino-3-phenyl-1,2,4-thiadiazole are added to the reaction mixture and the further 60 parts of the mixture of 50 parts acetic acid and 50 parts phosphoric acid is added thereto and stirring is effected at the same temperature for 21/2 hours.

After clarification the clear yellow diazo solution is added dropwise to an aqueous solution consisting of 39.1 parts of the coupling component of the formula ##STR149## in 300 parts water including 2 parts sodium acetate and 5 parts aminosulphonic acid. The mixture is stirred for 1 hour and the pH of the solution is adjusted to a value from 4 to 5 by the addition of sodium hydroxide; then, with the addition of 30 parts sodium chloride, the dye of the formula ##STR150## is salted out. After filtering, washing with a dilute brine solution, drying and grinding, 51 parts of a red powder is obtained which fast bluish-red dyeings on polyacrylonitrile and acid-modified polyester and polyamide fibres.

EXAMPLE 226

In place of the coupling component used in Example 225, 39.9 parts of the compound of the formula ##STR151## is used to obtain a similar dye of the formula ##STR152## which on polyacrylonitrile as well as on acid-modified polyamide and polyester fibres gives fast dyeings of a yellowish red shade.

The structural composition of further dyes is shown in the following Table V. They can be in accordance with the process of Examples 225 and 226 and correspond with the formula ##STR153## in which R₃ ' to R₅ ', R₁₂ ' and K⁺ have the significances as shown in the columns. A further column I indicates the dye-shade on polyacrylonitrile. The anion A⁻ may be any one of those named in the foregoing description.

                                      Table V                                      __________________________________________________________________________     Ex.                                                                               R'.sub.3                                                                           R'.sub.                                                                            R'.sub.12  K.sup.⊕                                                                       R'.sub.4                                                                             I                                               __________________________________________________________________________     227                                                                               H   H                                                                                   ##STR154##                                                                               K.sub.1                                                                           C.sub.2 H.sub.5                                                                      yellowish- red                                  228                                                                               H   H   "          K.sub.2                                                                           "     "                                               229                                                                               H   H   "          K.sub.12                                                                          "     "                                               230                                                                               H   H   "          K.sub.13                                                                          "     "                                               231                                                                               H   H   "          K.sub.14                                                                          "     "                                               232                                                                               H   H   "          K.sub.15                                                                          "     "                                               233                                                                               H   H   "          K.sub.16                                                                          "     "                                               234                                                                               H   H   "          K.sub.17                                                                          "     "                                               235                                                                               H   H   "          K.sub.18                                                                          "     "                                               236                                                                               H   H   "          K.sub.19                                                                          "     "                                               237                                                                               H   H   "          K.sub.35                                                                          "     "                                               238                                                                               H   H   "          K.sub.36                                                                          "     "                                               239                                                                               H   H   "          K.sub.37                                                                          "     "                                               240                                                                               H   H   "          K.sub.43                                                                          "     "                                               241                                                                               H   H   "          K.sub.44                                                                          "     "                                               242                                                                               H   CH.sub.3                                                                           "          K.sub.1                                                                           CH.sub.3                                                                             "                                               243                                                                               H   "   "          K.sub.2                                                                           "     "                                               244                                                                               H   "   "          K.sub.12                                                                          "     "                                               245                                                                               H   "   "          K.sub.13                                                                          "     "                                               246                                                                               H   "   "          K.sub.14                                                                          "     "                                               247                                                                               H   "   "          K.sub.15                                                                          "     "                                               248                                                                               H   "   "          K.sub.16                                                                          "     "                                               249                                                                               H   "   "          K.sub.17                                                                          "     "                                               250                                                                               H   "   "          K.sub.18                                                                          "     "                                               251                                                                               H   "   "          K.sub.19                                                                          "     "                                               252                                                                               H   "   "          K.sub.35                                                                          "     "                                               253                                                                               H   "   "          K.sub.36                                                                          "     "                                               254                                                                               H   "   "          K.sub.37                                                                          "     "                                               255                                                                               H   "   "          K.sub.43                                                                          "     "                                               256                                                                               H   "   "          K.sub.44                                                                          "     "                                               257                                                                               CH.sub.3                                                                           H                                                                                   ##STR155##                                                                               K.sub.1                                                                           C.sub.2 H.sub.5                                                                      bluish- red                                     258                                                                               "   H   "          K.sub.3                                                                           "     "                                               259                                                                               "   H   "          K.sub.12                                                                          "     "                                               260                                                                               "   H   "          K.sub.13                                                                          "     "                                               261                                                                               "   H   "          K.sub.14                                                                          "     "                                               262                                                                               "   H   "          K.sub.15                                                                          "     "                                               263                                                                               "   H   "          K.sub.16                                                                          C.sub.2 H.sub.5                                                                      "                                               264                                                                               "   H   "          K.sub.17                                                                          "     "                                               265                                                                               "   H   "          K.sub.18                                                                          ""                                                    266                                                                               "   H   "          K.sub.19                                                                          "     "                                               267                                                                               "   H   "          K.sub.35                                                                          "     "                                               268                                                                               "   H   "          K.sub.36                                                                          "     "                                               269                                                                               "   H   "          K.sub.37                                                                          "     "                                               270                                                                               "   H   "          K.sub.43                                                                          "     "                                               271                                                                               "   H   "          K.sub.44                                                                          "     "                                               272                                                                               "   H                                                                                   ##STR156##                                                         273                                                                               "   H                                                                                   ##STR157##                                                                               K.sub.2                                                                           "     "                                               274                                                                               "   H                                                                                   ##STR158##                                                                               K.sub.2                                                                           "     "                                               275                                                                               "   H                                                                                   ##STR159##                                                                               K.sub.2                                                                           "     "                                               276                                                                               "   H   CH.sub. 3 SO.sub.2                                                                        K.sub.2                                                                           "     "                                               277                                                                               "   H   CH.sub.3SO K.sub.2                                                                           "     "                                               278                                                                               "   H   CH.sub.3S  K.sub.2                                                                           "     "                                               279                                                                               CH.sub.3                                                                           H   Cl         K.sub.2                                                                           C.sub.2 H.sub.5                                                                      red                                             280                                                                               "   H   CH.sub.3   K.sub.2                                                                           "     "                                               281                                                                               H   CH.sub.3                                                                            ##STR160##                                                                               K.sub.2                                                                           CH.sub.3                                                                             yellowish- red                                  282                                                                               H   "                                                                                   ##STR161##                                                                               K.sub.2                                                                           C.sub.4 H.sub.9                                                                      "                                               283                                                                               H   "   "          K.sub.2                                                                           C.sub.2 H.sub.4 CN                                                                   orange                                          284                                                                               H   "   "          K.sub.4                                                                           CH.sub.3                                                                             yellowish-                                                                     red                                             __________________________________________________________________________     285                                                                                ##STR162##                                                                 286                                                                                ##STR163##                                                                 287                                                                                ##STR164##                                                                 288                                                                                ##STR165##                                                                 289                                                                                ##STR166##                                                                 290                                                                                ##STR167##                                                                 291                                                                                ##STR168##                                                                 292                                                                                ##STR169##                                                                 293                                                                                ##STR170##                                                                 294                                                                                ##STR171##                                                                 295                                                                                ##STR172##                                                                 __________________________________________________________________________

EXAMPLE 296

94.8 Parts 1-methylamino-4-bromoanthraquinone and 1 part copper acetate are added to 90 parts 1-dimethylamino-3-aminopropane and are stirred at 90° to 100° until the condensation reaction is finished as determined by thin-layer chromatography. The mixture is diluted with water until the reaction product begins to separate out. After cooling, the blue dye is filtered with suction, washed with neutral water and dried.

50.5 Parts of the fine pulverized dye so obtained is dissolved in 1000 parts dichlorobenzene and mixed with 31.2 parts 1-phenoxy-2-chloroethane, at 150° and is afterwards stirred at this temperature for 1 hour. After cooling the separated dye is filtered with suction, washed with toluene and dried under vacuum at 50° to 60°. 53 Parts of blue dye of the formula ##STR173## are obtained which dye gives fast blue dyeings on polyacrylonitrile and acid-modified polyamide fibres.

EXAMPLE 297

In place of 1-phenoxy-2-chloroethane as used in Example 296, 36 parts 1-phenoxy-4-chlorobutene-2 is used, employing the same procedure as described in Example 296, to obtain a similar dye of the formula ##STR174## which on polyacrylonitrile and acid-modified polyamide fibres gives fast dyeings of a blue shade.

The structural composition of further dyes is shown in the following Table VI. The dyes may be obtained according to the procedure of the processes hereinbefore described and they correspond with the formula ##STR175## in which R₁₃ ' to R₁₅ ', K⁺ and X have the significances as shown in the columns of the Table. A further column indicates the dye shade on polyacrylonitrile. The anion A⁻ may be any one of those named in the foregoing description.

                  Table VI                                                         ______________________________________                                         Ex.  R'.sub.14 R'.sub.15                                                                              X   K.sup.⊕                                                                         R'.sub.13 I                                    ______________________________________                                         298  H         H       1   K.sub.2                                                                             CH.sub.3  blue                                 299  H         H       1   K.sub.13                                                                            "         "                                    300  H         H       1   K.sub.17                                                                            "         "                                    301  H         H       1   K.sub.18                                                                            "         "                                    302  H         H       1   K.sub.19                                                                            "         "                                    303  H         H       1   K.sub.35                                                                            "         "                                    304  H         H       1   K.sub.43                                                                            "         "                                    305  H         H       1   K.sub.46                                                                            "         "                                    306  H         H       1   K.sub.2                                                                              ##STR176##                                                                              "                                    307  H         OH      1   K.sub.2                                                                             CH.sub.3  "                                    308  H         H       2   K.sub.2                                                                             "         "                                    309  H         H       1   K.sub.1                                                                              ##STR177##                                                                              greenish- blue                       310  H         H       1   K.sub.2                                                                             "         "                                    311  H         H       1   K.sub.13                                                                            "         "                                    312  H         H       1   K.sub.17                                                                            "         "                                    313  H         H       1   K.sub.18                                                                            "         "                                    314  H         H       1   K.sub.19                                                                            "         "                                    315  H         H       1   K.sub.35                                                                            "         "                                    316  H         H       1   K.sub.44                                                                            "         "                                    317  H         H       1   K.sub.46                                                                             ##STR178##                                                                              greenish- blue                       318  H         OH      1   K.sub.2                                                                             "         "                                    319  CN        H       1   K.sub.2                                                                             CH.sub.3  "                                    320  CONH.sub.2                                                                               H       1   K.sub.2                                                                             "         "                                    321  Br        H       1   K.sub.2                                                                             "         "                                    ______________________________________                                    

EXAMPLE 322

40.5 Parts of monochloromethylated 1-methylamino-4-(2',4'-xylidine)-anthraquinone, (obtained by reacting 1-methylamino-4-(2',4'-xylidene)-anthraquinone with dichlorodimethylether) are dissolved in 450 parts methanol at 50° and at this temperature is added dropwise to a solution of 15 parts diethylamine in 40 parts methanol. The solution is heated to its boiling point and then cooled to 40°, and a solution of 15.7 parts 2-phenoxy-1-chloroethane in 30 parts methanol are added thereto. The mixture is heated to its boiling point and then left to cool. The precipitated dye is filtered and washed with 50 parts methanol. After drying 41.4 parts of a dye of the formula ##STR179## is obtained which on polyacrylonitrile and acid-modified polyester and polyamide fibres gives fast dyeings of a greenish-blue shade.

The structural composition of further dyes is given in the following Table VII. They can be prepared in accordance with the procedure of Example 322 and correspond to the formula ##STR180## in which R₁₃ ', R₁₆ ', Y and K⁺ have the significances as shown in the columns. A further column I indicates the shade of dyeing obtained on polyacrylonitrile. The anion A⁻ may be any one of these named in the foregoing description.

                  Table VII                                                        ______________________________________                                         Ex.  R'.sub.13                                                                              R'.sub.16                                                                              K.sup.⊕                                                                         Y          I                                         ______________________________________                                         323  H       H       K.sub.2                                                                             CH.sub.2   reddish-blue                              324  H       H       K.sub.13                                                                            "          "                                         325  H       H       K.sub.17                                                                            "          "                                         326  H       H       K.sub.18                                                                            "          "                                         327  H       H       K.sub.19                                                                            "          "                                         328  H       H       K.sub.35                                                                            "          "                                         329  H       H       K.sub.43                                                                            CH.sub.2   reddish-blue                              330  H       H       K.sub.44                                                                            "          "                                         331  H       H       K.sub.1                                                                             OC.sub.2 H.sub.4                                                                          "                                         332  H       H       K.sub.2                                                                             "          "                                         333  H       H       K.sub.13                                                                            "          "                                         334  H       H       K.sub.17                                                                            "          "                                         335  H       H       K.sub.18                                                                            "          "                                         336  H       H       K.sub.19                                                                            "          "                                         337  H       H       K.sub.35                                                                            "          "                                         338  H       H       K.sub.43                                                                            "          "                                         339  H       H       K.sub.44                                                                            "          "                                         340  H       H       K.sub.45                                                                            CH.sub.2   "                                         341  H       H       K.sub.46                                                                            "          "                                         342  H       H       K.sub.45                                                                            OC.sub.2 H.sub.4                                                                          "                                         343  H       H       K.sub.46                                                                            "          "                                         344  CH.sub.3                                                                               CH.sub.3                                                                               K.sub.1                                                                             CH.sub.2   greenish-blue                             345  "       "       K.sub.2                                                                             "          "                                         346  "       "       K.sub.13                                                                            "          "                                         347  "       "       K.sub.17                                                                            "          "                                         348  "       "       K.sub.18                                                                            "          "                                         349  "       "       K.sub.19                                                                            "          "                                         350  "       "       K.sub.35                                                                            "          "                                         351  "       "       K.sub.43                                                                            "          "                                         352  "       "       K.sub.44                                                                            "          "                                         353  "       "       K.sub.45                                                                            "          "                                         354  "       "       K.sub.46                                                                            "          "                                         355  "       "       K.sub.4                                                                             "          "                                         ______________________________________                                    

The structural composition of further dyes is shown in the following Table VII. They may be prepared in accordance with the procedure of the foregoing Examples and correspond with the formula ##STR181## in which Y₁ ', R₁₇ ' to R₂₀ ' and K⁺ have the significances as shown in the columns. A further column I indicates the shade on dyeing on polyacrylonitrile. The anion A⁻ may be any one of those named in the foregoing description.

                                      Table VIII                                   __________________________________________________________________________     Ex.                                                                               R'.sub.17                                                                           R'.sub.18                                                                          R'.sub.19                                                                           R'.sub.20                                                                              Y.sub.1      K.sup. ⊕                                                                          I                                 __________________________________________________________________________     356                                                                               H    H   NH.sub.2                                                                            NHCH.sub.3                                                                             CONHC.sub.2 H.sub.4                                                                         K.sub.2                                                                              greenish-                                                                      blue                               357                                                                               H    H   "                                                                                    ##STR182##                                                                            OC.sub.2 H.sub.4                                                                            K.sub.2                                                                              bluish violet                      358                                                                               OH   NH.sub.2                                                                           "    OH                                                                                      ##STR183##  K.sub.2                                                                              blue                               359                                                                               H    H   "    NHCH.sub.3                                                                             CONHC.sub.3 H.sub.7                                                                         K.sub.6                                                                              greenish                                                                       blue                               360                                                                                ##STR184##                              blue                               361                                                                                ##STR185##                              red                                362                                                                                ##STR186##                              red                                363                                                                                ##STR187##                              blue                               364                                                                                ##STR188##                              yellow                             __________________________________________________________________________

APPLICATION EXAMPLE A

20 Parts of the salt of the dye described in Example 1 and 80 parts dextrin are ground for 4 hours in a powder mill. 1 Part of the preparation so obtained is made into a paste with 1 part 40% acetic acid, then 200 parts demineralized water are poured onto the paste and the mixture is boiled for a short time. (The same dye and dextrin mixture can also be formed into a paste with 100 parts water and finally be spray dried.) The mixture is then diluted with 7000 parts demineralized water, mixed with 2 parts glacial acetic acid and is put into a bath at 60° with 100 parts polyacrylonitrile fabric. The fabric may be pretreated for 10 to 15 minutes at 60° in a bath consisting of 8000 parts water and 2 parts glacial acetic acid.

The dye bath is raised to 98° to 100° over a period of 30 minutes, boiled for 11/2 hours and the fabric is rinsed. A bluish-red dyeing with good light and wet fastness properties is obtained.

10 Parts of the dye mentioned in Example 1 are dissolved in 60 parts glacial acetic acid and 30 parts water. A stable concentrated solution, with a dye content of about 10%, is obtained, which solution can be used to dye polyacrylonitrile according to the above-mentioned process.

APPLICATION EXAMPLE B

20 Parts of the dye from Example 1 are mixed with 80 parts dextrin in a ball-mill for 48 hours; 1 part of the preparation so obtained is made into a paste with 1 part 40% acetic acid, 200 parts demineralized water are poured onto the paste and the mixture is boiled for a short time. With this solution the following dyeings are made:

a. The solution is diluted with 7000 parts of demineralized water and mixed with 21 parts of anhydrous sodium sulphate, 14 parts of ammonium sulphate, 14 parts of formic acid and 15 parts of a carrier, based on the reaction product of ethylene oxide with dichlorophenolene are put into a bath at 60° with 100 parts of a polyester fabric, which fabric has been modified with acid groups. The fabric may be pretreated for 10 to 15 minutes at 60° in a bath consisting of 8000 parts of water and 2 parts of glacial acetic acid.

The dyebath is raised to 98°-100° over a period of 30 minutes, boiled for 11/2 hours and the fabric rinsed. A similar bluish-red dyeing with good wet fastness is obtained.

b. The solution is diluted with 3000 parts of demineralized water and mixed with 18 parts of anhydrous sodium sulphate, together with 6 parts of ammonium sulphate and formic acid and put into the bath at 60° with 100 parts of a polyester fabric, which fabric has been modified with acid groups. The closed vessel is heated to 110° over a period of 45 minutes, kept at this temperature for 1 hour with shaking, cooled to 60° within 25 minutes and the dyed fabric rinsed. A similar bluish-red dyeing with good wet fastness is obtained.

c. The same procedure as described in paragraph (b) above is carried out except that the closed vessel is heated for 1 hour at 120°.

Formulae of representative dyes of the foregoing Examples are as follows: ##STR189## 

What is claimed is:
 1. A dye of the formulawherein G is the residue of a carbocylic monoazodye R is alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl, amino or alkoxy of 1 to 4 carbon atoms, R₁ is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl, R₂ is hydrogen or alkyl of 1 to 4 carbon atoms, R₃ is hydrogen or alkyl of 1 to 4 carbon atoms, Q is ##STR190## wherein n R₇ is ##STR191## wherein each R₈ is independently alkyl of 1 to 4 carbon atoms, each R₉ is independently hydroxy, halo, alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy, alkoxy of 1to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy, cycloalkyl of 5 or 6 carbon atoms, cycloalkyl of 5 or 6 carbon atoms substituted by alkyl of 1 to 4 carbon atoms, trifluoromethyl, cyano, nitro, phenoxy, naphthyloxy, -CO-Ro, --CO-O-Ro, --O-CO-Ro, --CO-NH-Ro, --CO-N(Ro)₂, --O-CO-N(Ro)₂, -NH-CO-Ro, --SO₂ -Ro, -SO₂ -NH-Ro or -O-SO₂ -N(Ro)₂, wherein each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl, R₁₀ is hydrogen, halo or alkyl of 1to 4 carbon atoms, R₁₁ is hydrogen alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenoxy, halo, trifluoromethyl, nitro, cyano, -CO-Ro, --CO-O-Ro, --O-CO-Ro, --CO-NH-Ro, --NH-CO-Ro, -SO₂ -Ro --SO₂ --NH-Ro or -SO₂ -N)Ro)₂,wherein each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl, and a is 0, 1, 2, 3, 4, or 5, with the proviso that when a is 4 or 5 each R₉ must be halo, Y is ##STR192## wherein each R₄ is independently hydrogen or alkyl of 1 to 4 carbon atoms, R₅ is ##STR193## --SO--, --SO₂ --or --CO--, wherein R₆ is hydrogen or alkyl of 1 to 4 carbon atoms, and x is 1 to 6, and A⁻ is an anion,wherein each halo is independently chloro, bromo or iodo, with the proviso that the molecule is free of sulfo groups.
 2. A dye according to claim 1 wherein R is alkyl of 1 to 4 carbon atoms, and R₁ is alkyl of 1 to 4 carbon atoms.
 3. A dye according to claim 2 wherein R₂ is hydrogen or methyl, and R₃ is hydrogen or methyl.
 4. A dye according to claim 3 wherein Y is ##STR194## --CH₂ O-CH₂ CH₂ --, whereinR₄ is hydrogen or alkyl of 1 to 4 carbon atoms, and x' is 1, 2 or
 3. 5. A dye according to claim 4wherein Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.
 6. A dye according to claim 1 having the formula ##STR195## wherein D is a diazo component radical,K is a coupling component radical,each T" is independently ##STR196## W is a bridging group, q is 0 or 1, and t is 1 or 2,with the proviso that each --Wa-T" independently is bound to D or K.
 7. A dye according to claim 6 having the formula ##STR197## wherein Ka' is a coupling component radical,Z is -CO- or SO₂, T" is ##STR198## and t is 1 or
 2. 8. A compound of the formula ##STR199## wherein R₁₆ is hydrogen, phenyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl, phenoxy, alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, benzoyloxy, --CO-N-(Ra)₂ or --O-CO-N(Ra)₂, wherein each Ra is independently hydrogen or alkyl of 1 to 4 carbon atoms,R₁₇ is ##STR200## wherein R₂₅ is hydrogen or alkyl of 1 to 4 carbon atoms, R₁₉ is hydrogen, nitro, halo, cyano, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, -CO-Ro, --COORo, --CO--NHRo or -SO₂ -N(R₂₁)₂,wherein each R₂₁ is independently alkyl of 1 to 4 carbon atoms, and Ro is alkyl of 1 to 4 carbon atoms or phenyl,each of R₁₁₉ and R'₁₁₉ is independently hydrogen, nitro, halo, cyano, alkyl of 1 to 4 carbon atoms, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, R₂₁₉ is hydrogen, halo, nitro or cyano, with the proviso that at least one of R₁₉, R₁₁₉, R'₁₁₉ and R₂₁₉ is hydrogen or halo K' is ##STR201## wherein R₁₈ is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, Ka' is ##STR202## wherein each of R₁₈ ' and R₁₉ ' is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R₁₈ ' and R₁₉ ' is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl, R₂₁ ' is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, R₂₄ ' is hydroxy, amino or anilino, andeach of R₁₈₁ and R₁₉₁ is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that at least one of R₁₈₁ and R₁₉₁ is hydrogen or alkyl of 1 to 4 carbon atoms, Ka" is ##STR203## wherein each of R₁₈ ' and R₁₉ ' is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R₁₈ ' and R₁₉ ' is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl, and R₂₁ ' is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, Z is --CO- or --SO₂, t is 1 or 2, Hal is halo, and T" is ##STR204## wherein R is alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl, amino or alkoxy of 1 to 4 carbon atoms, R₁ is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by hydroxy or phenyl, R₂ is hydrogen or alkyl of 1 to 4 carbon atoms, R₃ is hydrogen or alkyl of 1 to 4 carbon atoms, Q is ##STR205## wherein R₇ is ##STR206## wherein each R₈ is independently alkyl of 1 to 4 carbon atoms,each R₉ is independently hydroxy; halo; alkyl of 1 to 4 carbon atoms; alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy; alkoxy of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl or phenoxy; cycloalkyl of 5 or 6 carbon atoms; cycloalkyl of 5 or 6 carbon atoms substituted by alkyl of 1 to 4 carbon atoms; trifluoromethyl; cyano; nitro; phenoxy; naphthyloxy; --CO--Ro; --CO--O--Ro; --O--CO--Ro; --CO--NH--Ro; --CO--N(Ro)₂ ; --O--CO--N(Ro)₂ ; --NH--CO--Ro; --SO₂ --Ro; --SO₂ --NH--Ro or --O--SO₂ --N(Ro)₂,wherein each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl, R₁₀ is hydrogen, halo or alkyl of 1 to 4 carbon atoms, R₁₁ is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl, phenoxy, halo, trifluoromethyl, nitro, cyano, --CO--Ro, --CO--O--Ro, --O--CO--Ro, --CO--NH--Ro, --NH--CO--Ro, --SO₂ --Ro, --SO₂ --NH--Ro or --SO₂ --N(Ro)₂,wherein each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl, and a is 0,
 1. 2, 3, 4, or 5, with the proviso that when a is 4 or 5 each R₉ must be halo, Y is ##STR207## wherein each R₄ is independently hydrogen or alkyl of 1 to 4 carbon atoms, R₅ is ##STR208## --SO--, --SO₂ -- or --CO--, wherein R₆ is hydrogen or alkyl of 1 to 4 carbon atoms, and x is 1 to 6, and A⁻ is an anion,wherein each halo is independently chloro, bromo or iodo.
 9. A compound according to claim 8 having the formula ##STR209## wherein R₁₆ is hydrogen, phenyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenyl, phenoxy, alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, benzoyloxy, --CO--N(Ra)₂ or --O--CO--2,R₁₇ is ##STR210## wherein R₂₅ is hydrogen or alkyl of 1 to 4 carbon atoms, R₁₉ is hydrogen, nitro, halo, cyano, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, --CO--Ro, --COORo, --CO--NHRo or --SO₂ --N(R₂₁)₂, wherein each R₂₁ is independently alkyl of 1 to 4 carbon atoms. each of R₁₁₉ and R'₁₁₉ is independently hydrogen, nitro, halo, cyano, alkyl of 1 to 4 carbon atoms, trifluoromethyl, alkylsulfonyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, R₂₁₉ is hydrogen, halo, nitro or cyano, with the proviso that at least one of R₁₉, R₁₁₉, R'₁₁₉ and R₂₁₉ is hydrogen, K' is ##STR211## wherein R₁₈ is hydrogen or halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, and T" is ##STR212## wherein each Ra is independently hydrogen or alkyl of 1 to 4 carbon atoms, and each Ro is independently alkyl of 1 to 4 carbon atoms or phenyl.
 10. A compound according to claim 9 wherein ##STR213## wherein Ra' is hydrogen, halo, nitro or cyano,Ra" is hydrogen or halo, each Ra'" is independently hydrogen or halo, and each of R_(1a) and R_(2a) is independently alkyl of 1 to 4 carbon atoms.
 11. A compound according to claim 10 wherein R₁₆ is alkyl of 1 to 4 carbon atoms, R₂₅ is hydrogen or methyl, andK' is ##STR214##
 12. A compound according to claim 11wherein R₁₆ is methyl or ethyl, R₁₈ is hydrogen or methyl, and R₂₅ is hydrogen.
 13. A compound according to claim 9wherein R is alkyl of 1 to 4 carbon atoms, R₁ is alkyl of 1 to 4 carbon atoms, R₂ is hydrogen or methyl, and R₃ is hydrogen or methyl.
 14. A compound according to claim 13wherein Y is ##STR215## --CH═CH--CH₂ --, --C|C--CH₂ -- or --CH₂ --O--CH₂ --CH₂ --, wherein R₄ is hydrogen or alkyl of 1 to 4 carbon atoms, and x' is 1, 2 or
 3. 15. A compound according to claim 14wherein Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.
 16. A compound according to claim 15wherein R is methyl or ethyl, R₁ is methyl or ethyl, R₂ is hydrogen, R₃ is hydrogen, R₄ is hydrogen or methyl, and x' is
 1. 17. A compound according to claim 16wherein Q is phenyl, 2-naphthyl or phenyl substituted by 1 to 5 chloro substituents, and Y is --CH₂ --.
 18. A compound according to claim 8 having the formula ##STR216## wherein Ka' is ##STR217## wherein each of R'₁₈ and R'₁₉ is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R'₁₈ and R'₁₉ is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl,R'₂₁ is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, R'₂₄ is hydroxy, amino or anilino, andeach of R₁₈₁ and R₁₉₁ is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that at least one of R₁₈₁ and R₁₉₁ is hydrogen or alkyl of 1 to 4 carbon atoms, Z is --CO-- or --SO₂ t is 1 or 2, and T" is ##STR218##
 19. A compound according to claim 18wherein R is alkyl of 1 to 4 carbon atoms, R₁ is alkyl of 1 to 4 carbon atoms, R₂ is hydrogen or methyl, and R₃ is hydrogen or methyl.
 20. A compound according to claim 19wherein Y is ##STR219## --CH═--CH₂ --, --C|C--CH₂ -- or --CH₂ --O--CH₂ --CH₂ --,wherein R₄ is hydrogen or alkyl of 1 to 4 carbon atoms, and x' is 1, 2 or
 3. 21. A compound according to claim 20wherein Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.
 22. A compound according to claim 21wherein R is methyl or ethyl, R₁ is methyl or ethyl, R₂ is hydrogen, R₃ is hydrogen, R₄ is hydrogen or methyl, and x' is
 1. 23. A compound according to claim 22wherein Q is phenyl, 2-naphthyl or phenyl substituted by 1 to 5 chloro substituents, and Y is --CH₂ --.
 24. A compound according to claim 8 having the formula ##STR220## wherein Ka" is ##STR221## wherein each of R'₁₈ and R'₁₉ is independently hydrogen, phenyl, cyclohexyl, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by alkoxycarbonyl wherein the alkoxy moiety has 1 to 4 carbon atoms, benzoyloxy, phenoxy, halo, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkylcarbonyloxy wherein the alkyl moiety has 1 to 4 carbon atoms or N,N-dialkylamino wherein each alkyl independently has 1 to 4 carbon atoms, with the proviso that when one of R'₁₈ and R'₁₉ is phenyl or cyclohexyl, the other is other than phenyl or cyclohexyl, andR'₂₁ is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo, Hal is halo, and T" is ##STR222##
 25. A compound according to claim 24wherein R is alkyl of 1 to 4 carbon atoms, R₁ is alkyl of 1 to 4 carbon atoms, R₂ is hydrogen or methyl, and R₃ is hydrogen or methyl.
 26. A compound according to claim 25wherein Y is ##STR223## --CH═CH--CH₂ --, --C|C--CH₂ -- or --CH₂ --O--CH₂ --CH₂ --,wherein R₄ is hydrogen or alkyl of 1 to 4 carbon atoms, and x' is 1, 2 or
 3. 27. A compound according to claim 26wherein Q is phenyl, naphthyl, biphenylyl, phenyl substituted by halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, trifluoromethyl, cyano or nitro or phenyl substituted by 2 to 5 chloro substituents.
 28. A compound according to claim 27wherein R is methyl or ethyl, R₁ is methyl or ethyl, R₂ is hydrogen, R₃ is hydrogen, R₄ is hydrogen or methyl, and x' is
 1. 29. A compound according to claim 28wherein Q is phenyl, 2-naphthyl or phenyl substituted by 1 to 5 chloro substituents, and Y is --CH₂ --.
 30. A compound according to claim 11 having the formula ##STR224##
 31. A compound according to claim 11 having the formula ##STR225##
 32. A compound according to claim 11 having the formula ##STR226##
 33. A compound according to claim 11 having the formula ##STR227##
 34. The compound according to claim 33 wherein A⁻ is Cl⁻.
 35. A compound according to claim 11 having the formula ##STR228##
 36. The compound according to claim 35 wherein A⁻ is Cl⁻.
 37. A compound according to claim 11 having the formula ##STR229##
 38. The compound according to claim 37 wherein A⁻ is Cl⁻.
 39. A compound according to claim 11 having the formula ##STR230##
 40. The compound according to claim 39 wherein A⁻ is Cl⁻.
 41. A compound according to claim 11 having the formula ##STR231##
 42. The compound according to claim 41 wherein A⁻ is Cl⁻.
 43. A compound according to claim 11 having the formula ##STR232##
 44. The compound according to claim 43 wherein A⁻ is Cl⁻.
 45. A compound according to claim 11 having the formula ##STR233##
 46. A compound according to claim 11 having the formula ##STR234##
 47. A compound according to claim 11 having the formula ##STR235##
 48. The compound according to claim 47 wherein A⁻ is Cl⁻.
 49. A compound according to claim 11 having the formula ##STR236##
 50. The compound according to claim 49 wherein A⁻ is Cl⁻.
 51. A compound according to claim 11 having the formula ##STR237##
 52. The compound according to claim 51 wherein A⁻ is Cl⁻.
 53. A compound according to claim 11 having the formula ##STR238##
 54. A compound according to claim 11 having the formula ##STR239##
 55. A compound according to claim 11 having the formula ##STR240##
 56. A compound according to claim 11 having the formula ##STR241##
 57. A compound according to claim 11 having the formula ##STR242##
 58. A compound according to claim 22 having the formula ##STR243##
 59. A compound according to claim 22 having the formula ##STR244##
 60. A compound according to claim 22 having the formula ##STR245##
 61. A compound according to claim 29 having the formula ##STR246##
 62. A compound according to claim 29 having the formula ##STR247## 